EP3034485B1 - Reaction of carbon dioxide with hydrogen using a permselective membrane - Google Patents

Reaction of carbon dioxide with hydrogen using a permselective membrane Download PDF

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EP3034485B1
EP3034485B1 EP15200377.8A EP15200377A EP3034485B1 EP 3034485 B1 EP3034485 B1 EP 3034485B1 EP 15200377 A EP15200377 A EP 15200377A EP 3034485 B1 EP3034485 B1 EP 3034485B1
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reaction
hydrogen
membrane
bar
layers
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German (de)
French (fr)
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EP3034485A1 (en
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Jörg GRÜTZNER
Dirk Martin
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Mum Screentec Filter- und Praisionstechnik Aus Metall GmbH
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Mum Screentec Filter- und Praisionstechnik Aus Metall GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel

Definitions

  • the present invention relates to a method for carrying out chemical equilibrium reactions using a permselective membrane. More particularly, the invention relates to a process for reacting carbon dioxide and hydrogen using a carbon membrane.
  • nickel, ruthenium, rhodium and cobalt are known, which are usually applied to an oxidic support such as SiO 2 , TiO 2 , MgO, Al 2 O 3 , La 2 O 3 , as for example in Ohya et al. 1997: Methanation of carbon dioxide by using membrane reactor integrated with water vapor permselective membrane and its analysis, Journal of Membrane Science 131 (1-2 ).
  • the most successful solution is currently the combination of 0.5% Ru on TiO 2.
  • high CO 2 conversions and CH 4 yields can be achieved at temperatures of ⁇ 300 ... 350 ° C (John Ralston (http : //www.pennenergy.com/index/power/display/0723256773/articles/pennenergy/ugc/renewable/the-sabatier-reaction.html).
  • the Sabatier reaction is a very demanding reaction as it is highly exothermic and, upon addition of the starting materials, depending on the degree of dilution with inert gases Temperatures above 600 ° C leads. This temperature level not only destroys some catalysts, for example, active centers are lost by, for. B. sintering Ni particles in the nm range together, but also shifts the reaction equilibrium in the direction of the reactants. By contrast, too low temperatures result in kinetic limitations of the reaction and the amount of desired products.
  • the Sabatier reaction is an exothermic equilibrium reaction, it is bag-end-blocked with increasing reaction or process temperature.
  • the removal of a reaction product directly from the reaction in the process causes an increase in the driving force for product formation.
  • a suitable water-separating membrane does just that by separating the reaction product water directly in the process.
  • a yield increase compared to the process without membrane is achieved.
  • by the separation of the water of reaction a Subsequent drying of the methane to achieve the feed quality superfluous and this process step can be saved.
  • methanol can be made from a syngas of carbon monoxide and hydrogen.
  • the yield can also be improved if it is possible to separate the water on the side of the products ( JP 2007055970 A ).
  • hydrophilic membranes For the separation of water from gas mixtures at a higher temperature usually hydrophilic membranes are used. These are in particular SiO 2 membranes and zeolite A membranes ( Wang et al., 2011: "Effects of water vapor on gas permeation and separation properties of MFI zeolite membranes at high temperatures, AIChE Journal 58 (1 ); Sano et al., 1994: “Separation of ethanol / water mixture by silicalite membrane on pervaporation, Journal of Membrane Science 95 (3 ); Hamzah et al., 2013: Pervaporation through NaA zeolite membranes - A review, The Third Basic Science International Conference 2013 ).
  • Preferred application is the dewatering and drying of solvent vapors.
  • SiO 2 membranes are subject to thermal degradation above 100 ° C. under reducing conditions, as present in the Sabatier reaction (US Pat.
  • the invention has for its object to propose a way to conduct process of equilibrium reactions in which on the side of the reaction products, water is separated and an improved yield of reaction products is achieved.
  • the object is achieved by a method for carrying out chemical equilibrium reactions in which carbon dioxide and hydrogen are reacted, using a permselective membrane, wherein the equilibrium reaction is either a Sabatier reaction or a methanol production reaction, and by action the permselective membrane amounts of at least one product obtained in the reaction are separated and removed from the reaction.
  • Characteristic of a method according to the invention is that a permselective membrane is used which consists of a material which has a porous structure with average pore sizes of less than 0.45 nm (4.5 ⁇ ) and whose material is hydrophobic at least on its free surfaces is. A material is considered to be hydrophobic if wetting angles of 85 ° and above are measured on an attached water droplet.
  • the chemical equilibrium reaction is carried out in the presence of a water-containing gas mixture.
  • a hydrous gas mixture is obtained, for example, by the products of the Sabatier reaction methane and water. Due to the high temperatures at which this equilibrium reaction takes place, the water is present as water vapor.
  • a mixture of methane and steam is understood as a gas mixture, in particular as a water-containing gas mixture.
  • the core of the invention is the use of an organic membrane composed essentially of carbon and / or of hydrocarbons.
  • the permselective membrane (henceforth also: membrane) is a carbon membrane.
  • the membrane can be applied, for example, on ceramic elements of different lengths and diameters, which act as a carrier.
  • the membranes may be present on an inner side and / or on an outer side of the carriers.
  • the carriers may have on the inside and / or on the outside intermediate layers of decreasing pore size, over which the membrane may be arranged.
  • Carriers have, for example, a length of 10 to 2000 mm, for example 105 mm and 250 mm.
  • the carriers can be coated on their inside and / or on their outside partially or completely with the membrane.
  • membranes can be made on any shaped carriers, for example, 10 to 2000 mm, for example, 500 mm in length.
  • one-sided closed ceramic carriers can be produced and the membrane can also be applied to these on the outside.
  • partially coated carrier is to ensure, for example, by a constructive measure that a separation of the water takes place only over the areas of the carrier, which are covered by the membrane.
  • the structure of the material is graphite-like and formed by layers of the material, the structure is formed by at least one sequence of the layers, wherein the layers are arranged in planes, there is a mean interlayer spacing of less than 0.45 nm (4.5 ⁇ ) between adjacent layers, and the sequence of layers is disordered turbostratically.
  • a membrane is used in which at least one metal-containing catalyst is applied to one surface of the permselective membrane.
  • applied means that the catalyst is connected to the membrane or is in direct contact with the membrane.
  • the catalyst is bound in the form of particles on a surface of the membrane and / or this is as bulk material or on.
  • the catalyst may also be present as a coating on the membrane or on parts of the membrane.
  • Catalysts may be metal-containing catalysts from a group comprising the metals ruthenium, nickel, cobalt, rhodium, platinum and palladium or their alloys.
  • the term metal-containing catalysts also includes metallic catalysts.
  • gases such as biogas, sewage gas, biomethane, molecular hydrogen-containing carbon dioxide streams, molecular hydrogen-releasing electrolyses, hydrogen streams, or combinations of these sources can be used to advantage.
  • the sources of molecular hydrogen are treated in terms of process technology before they are used in the process according to the invention.
  • they can be reduced and desulfurized to contain ⁇ 1 ppm of oxygen (02) and sulfur (S), ensuring feed-in quality.
  • the chemical equilibrium reaction is preferably either a Sabatier reaction or a methanol production reaction.
  • the process of the invention in particular the Sabatier reaction, is preferably carried out at a pressure selected from a range of 1 to 100 bar inclusive, e.g. B. 5, 75, 100 bar, and at a temperature selected from a range of 150 to 600 ° C inclusive, z. B. 400, 500 ° C performed.
  • the Sabatier reaction is carried out at a pressure selected from a range of 10 to 20 bar and at a temperature selected from a range of 250 to 450 ° C.
  • the Sabatier reaction can be carried out efficiently at a pressure of 20 bar and at a temperature of 300 ° C.
  • the chemical equilibrium reaction is a methanol production reaction, it is preferably conducted at a pressure selected from a range of 80 to 250 bar inclusive and at a temperature selected from a range of 150 to 400 ° C inclusive.
  • Methanol (CH 3 OH) is one of the most frequently produced organic chemicals and serves as the starting material for many other chemical products (eg formaldehyde, formic acid, etc.).
  • the technical production is carried out mainly by a catalytically assisted reaction of CO and H 2 .
  • the processes for methanol production are based on the prevailing reaction pressures in high pressure processes (250-350 bar, ⁇ 370 ° C), medium pressure (100-250 bar, ⁇ 220-300 ° C) and low pressure processes (50-100 bar, 200-300 ° C). Due to economic disadvantages, the high pressure process is no longer used today. It is widely used in the prior art copper-zinc catalysts on alumina.
  • the membranes can be used in flexible geometry.
  • the membranes allow selective separation of water under process conditions. Equipped with an active catalyst for the chemical equilibrium reaction to be carried out, the yield can be significantly increased and the achievement of the feed quality can be facilitated.
  • a catalyst used can be arranged as bulk material on the membrane or it is a catalytically active Membrane used.
  • Preferred use of the membrane is the conversion of carbon dioxide and hydrogen to methane (Sabatier reaction) or methanol.
  • the use according to the invention of the membranes described is used, for example, for the removal of water from the Sabatier reaction.
  • a direct contact between water-separating membrane and catalyst makes sense.
  • the separation-active membrane can serve as a catalyst carrier.
  • the catalyst or catalyst precursor is applied to the release-active layer and optionally activated in a suitable form, for example by heat. The activation of the catalyst takes place, for example, under the reaction conditions of the Sabatier reaction.
  • the use according to the invention of the membranes described also makes it possible to efficiently carry out a chemical equilibrium reaction in which methanol and water are recovered on the product side from carbon dioxide and hydrogen on the educt side.
  • the selective separation of water shifts the equilibrium towards the products and promotes the formation of methanol.
  • the catalyst used is an aluminum-supported nickel oxide, for example the commercially available product METH 134.
  • the catalyst was applied as a bed and activated accordingly in a stream of hydrogen / nitrogen (1: 9).
  • the educt volume flow is approximately 250 Nl / h (standard liters per hour).
  • the H 2 / CO 2 ratio is 4.1: 1 (19.6 vol% CO 2 , 80.4 vol% H 2 ) at a process pressure of 20 bar (20 bar overpressure) and reaction temperatures of 275-450 ° C , Revenues of between 85 and 89% are achieved with> 99% CH 4 selectivity.
  • the CH 4 yield is also between 85 and 89%.
  • the catalyst used is an aluminum-supported nickel oxide, for example the commercially available product METH 134 (manufacturer Clariant).
  • the catalyst was applied as a bed and activated in a hydrogen / nitrogen stream (1: 9) accordingly.
  • the educt volume flow is approximately 250 Nl / h in total.
  • the H 2 / CO 2 ratio is 4.1: 1 (19.6 vol% CO 2 , 80.4 vol% H 2 ) at a process pressure of 20 bar and reaction temperatures of 240-450 ° C.
  • the space velocity at the membrane is ⁇ 21.5 s -1 or corresponds to a linear velocity of ⁇ 0.04 m / s. Revenues> 90% are achieved with a CH 4 selectivity of> 99%.
  • the CH 4 yield is also> 90%.
  • catalyst precursor a coating of the membrane with nickel oxide is used. This precursor is reduced in a stream of hydrogen / nitrogen (1: 9) to the active metallic nickel and activated accordingly.
  • the educt volume flow is about 1000 Nl / h in total.
  • the H 2 / CO 2 ratio is 4.1: 1 (19.6 vol% CO 2 , 80.4 vol% H 2 ) at a process pressure of 20 bar and reaction temperatures of 240-450 ° C.
  • the space velocity at the membrane is ⁇ 58 s -1 or corresponds to a linear velocity of ⁇ 0.02 m / s. Revenues> 95% are achieved with a CH 4 selectivity of> 99%.
  • the CH 4 yield is also> 95%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Durchführung von chemischen Gleichgewichtsreaktionen unter Verwendung einer permselektiven Membran. Die Erfindung betrifft insbesondere ein Verfahren zur Umsetzung von Kohlendioxid und Wasserstoff unter Verwendung einer Kohlenstoffmembran.The present invention relates to a method for carrying out chemical equilibrium reactions using a permselective membrane. More particularly, the invention relates to a process for reacting carbon dioxide and hydrogen using a carbon membrane.

Die Umsetzung von Wasserstoff mit Kohlendioxid wird im Wesentlichen aus zwei Gründen verfolgt. Einerseits wird zunehmend Wasserstoff durch Elektrolyse hergestellt, um Netzschwankungen aus dem zunehmenden Anteil fluktuierenden Stroms aus regenerativen Quellen zu puffern ("power to gas"). Die Speicherung und die Verteilung von Wasserstoff können zu geringen Anteilen direkt im Erdgasnetz erfolgen. Durch die Umsetzung mit Kohlendioxid zu Methan wären die Speicherung und Verteilung in viel größerem Maßstab möglich. Der zweite Grund betrifft die chemische Bindung und Nutzung von Kohlendioxid und hat damit erhebliche umweit- und klimatechnische Vorteile.The reaction of hydrogen with carbon dioxide is pursued for essentially two reasons. On the one hand, hydrogen is increasingly being produced by electrolysis in order to buffer power fluctuations from the increasing proportion of fluctuating electricity from regenerative sources ("power to gas"). The storage and distribution of hydrogen can be done in small proportions directly in the natural gas network. By converting carbon dioxide to methane, storage and distribution would be possible on a much larger scale. The second reason concerns the chemical binding and use of carbon dioxide and thus has considerable environmental and environmental advantages.

In der dem Fachmann bekannten Sabatier-Reaktion, die eine chemische Gleichgewichtsreaktion ist, werden Kohlendioxid (CO2) und Wasserstoff (H2) (Edukte) zu Methan (CH4) und Wasser (H2O) (Produkte) umgesetzt. Die Sabatier-Reaktion wird meist bei Drücken von ∼1...3 bara (absoluter Druck; bar absolut), vereinzelt auch bei höheren Drücken von bis zu 15 bara, und in einem Temperaturbereich von rund 200 bis 450 °C durchgeführt. Als geeignete Katalysatoren für diese Reaktion sind beispielsweise Nickel, Ruthenium, Rhodium und Cobalt bekannt, die meist auf einem oxidischen Träger wie SiO2, TiO2, MgO, Al2O3, La2O3 aufgebracht sind, wie dies beispielsweise in Ohya et al. 1997: Methanation of carbon dioxide by using membrane reactor integrated with water vapor permselective membrane and its analysis, Journal of Membrane Science 131 (1-2 ), beschrieben ist. Am erfolgreichsten stellt sich wohl momentan die Kombination 0,5 % Ru auf TiO2 dar. Abhängig vom Katalysator können hohe CO2-Umsätze und CH4-Ausbeuten bei Temperaturen von ∼300... 350°C erreicht werden (John Ralston (http://www.pennenergy.com/index/power /display/0723256773/articles/pennenergy/ugc/renewable/the-sabatier-reaction.html).In the Sabatier reaction known to those skilled in the art, which is a chemical equilibrium reaction, carbon dioxide (CO 2 ) and hydrogen (H 2 ) (starting materials) are converted to methane (CH 4 ) and water (H 2 O) (products). The Sabatier reaction is usually carried out at pressures of ~1 ... 3 bara (absolute pressure, bar absolute), occasionally even at higher pressures of up to 15 bara, and in a temperature range of about 200 to 450 ° C. As suitable catalysts for this reaction, for example, nickel, ruthenium, rhodium and cobalt are known, which are usually applied to an oxidic support such as SiO 2 , TiO 2 , MgO, Al 2 O 3 , La 2 O 3 , as for example in Ohya et al. 1997: Methanation of carbon dioxide by using membrane reactor integrated with water vapor permselective membrane and its analysis, Journal of Membrane Science 131 (1-2 ). The most successful solution is currently the combination of 0.5% Ru on TiO 2. Depending on the catalyst, high CO 2 conversions and CH 4 yields can be achieved at temperatures of ~ 300 ... 350 ° C (John Ralston (http : //www.pennenergy.com/index/power/display/0723256773/articles/pennenergy/ugc/renewable/the-sabatier-reaction.html).

Die Sabatier-Reaktion ist eine sehr anspruchsvolle Reaktion, da sie stark exotherm ist und nach Zugabe der Edukte, je nach Verdünnungsgrad mit inerten Gasen, zu Temperaturen über 600 °C führt. Dieses Temperaturniveau zerstört nicht nur manche Katalysatoren, beispielsweise gehen aktive Zentren verloren, indem z. B. Ni-Partikel im nm-Bereich zusammensintern, sondern verschiebt auch das Reaktionsgleichgewicht in Richtung der Edukte. Zu niedrige Temperaturen haben dagegen kinetische Limitierungen der Reaktion und der Menge der gewünschten Produkte zur Folge.The Sabatier reaction is a very demanding reaction as it is highly exothermic and, upon addition of the starting materials, depending on the degree of dilution with inert gases Temperatures above 600 ° C leads. This temperature level not only destroys some catalysts, for example, active centers are lost by, for. B. sintering Ni particles in the nm range together, but also shifts the reaction equilibrium in the direction of the reactants. By contrast, too low temperatures result in kinetic limitations of the reaction and the amount of desired products.

Verschiedene Publikationen behandeln bereits den Einsatz von Membranen. So führt der Einsatz einer Membran aus 20-fach beschichtetem hydrophilem porösem Glas auf einem keramischen Träger im besten Fall zu einer Erhöhung des CO2-Umsatzes um 18 % (bei 300°C, 0,2 MPa und Raumgeschwindigkeit = 0,0308 s-1) (Ohya et al.). Die Umsatzerhöhung ist dabei bemerkenswert, allerdings bewegt sich die Raumgeschwindigkeit weit unterhalb industriell notwendiger Bereiche von mindestens 3 s-1. Darüber hinaus werden Membranen vorgelagert zur eigentlichen Sabatier-Reaktion zum Aufkonzentrieren des Kohlendioxids eingesetzt ( Hwang et al. 2008: A membrane-based reactive separation system for CO2 removal in a life support system, Journal of Membrane Science 315 (1-2): 116 - 124 ). Berechnungen zeigen für diesen Fall synergetische Positiveffekte für die Reaktion. Aber auch weitere Prozesskonzepte sind möglich. Über die Fahrweise der Reaktion mit zwei hintereinander geschalteten Reaktoren mit zwischenzeitlichem Auskondensieren des Reaktionswassers kann der hier betrachtete Wasserstoffumsatz von ca. 90 % auf bis zu 99 % gesteigert werden ( Habazaki et al. 1998: Co-methanation of carbon monoxide and carbon dioxide on supported nickel and cobalt catalysts prepared from amorphous alloys, Applied Catalysis A: General 172 (1): 131 - 140 ). Die Trennung der Produkte Methan und Wasser ist für eine mögliche Einspeisung in das Erdgasnetz aber eine zwingende Vorrausetzung.Various publications already deal with the use of membranes. Thus, the use of a membrane of 20-fold coated hydrophilic porous glass on a ceramic support at best leads to an increase in the CO 2 conversion by 18% (at 300 ° C., 0.2 MPa and space velocity = 0.0308 s ). 1 ) (Ohya et al.). The increase in turnover is remarkable, but the space velocity is far below industrially necessary ranges of at least 3 s -1 . In addition, membranes are used upstream of the actual Sabatier reaction for concentrating the carbon dioxide ( Hwang et al. 2008: A membrane-based reactive separation system for CO2 removal in a life support system, Journal of Membrane Science 315 (1-2): 116-124 ). Calculations show synergistic positive effects for the reaction in this case. But other process concepts are possible. About the mode of operation of the reaction with two reactors connected in series with intermediate condensation of the water of reaction, the hydrogen conversion considered here can be increased from about 90% up to 99% ( Habazaki et al. 1998: Co-methanation of carbon monoxide and carbon dioxide supported nickel and cobalt catalysts prepared from amorphous alloys, Applied Catalysis A: General 172 (1): 131-140 ). The separation of the products methane and water is, however, a mandatory prerequisite for a possible feed-in into the natural gas network.

Da es sich bei der Sabatier-Reaktion um eine exotherme Gleichgewichtsreaktion handelt, ist sie mit zunehmender Reaktions- bzw. Prozesstemperatur ausbeutelimitiert. Der Entzug eines Reaktionsproduktes direkt aus der Reaktion im Prozess bewirkt eine Erhöhung der Triebkraft zur Produktbildung. Eine geeignete wasserabtrennende Membran bewirkt genau dies, indem das Reaktionsprodukt Wasser direkt im Prozess abgetrennt wird. So wird eine Ausbeutesteigerung verglichen zum Prozess ohne Membran erreicht. Weiterhin wird durch die Abtrennung des Reaktionswassers eine nachgeordnete Trocknung des Methans zur Erreichung der Einspeisequalität überflüssig und dieser Prozessschritt kann eingespart werden.Since the Sabatier reaction is an exothermic equilibrium reaction, it is bag-end-blocked with increasing reaction or process temperature. The removal of a reaction product directly from the reaction in the process causes an increase in the driving force for product formation. A suitable water-separating membrane does just that by separating the reaction product water directly in the process. Thus, a yield increase compared to the process without membrane is achieved. Furthermore, by the separation of the water of reaction a Subsequent drying of the methane to achieve the feed quality superfluous and this process step can be saved.

Methanol kann beispielsweise aus einem Synthesegas aus Kohlenmonoxid und Wasserstoff hergestellt werden. Insbesondere bei der Herstellung von Methanol aus Kohlendioxid und Wasserstoff als Edukte und Methanol und Wasser als Produkte einer chemischen Gleichgewichtsreaktion kann die Ausbeute ebenfalls verbessert werden, wenn es gelingt, das Wasser auf der Seite der Produkte abzutrennen ( JP 2007055970 A ).For example, methanol can be made from a syngas of carbon monoxide and hydrogen. In particular, in the production of methanol from carbon dioxide and hydrogen as starting materials and methanol and water as products of a chemical equilibrium reaction, the yield can also be improved if it is possible to separate the water on the side of the products ( JP 2007055970 A ).

Zur Abtrennung von Wasser aus Gasgemischen bei höherer Temperatur werden üblicherweise hydrophile Membranen eingesetzt. Dies sind insbesondere SiO2-Membranen und Zeolith-A-Membranen ( Wang et al., 2011: "Effects of water vapor on gas permeation and separation properties of MFI zeolite membranes at high temperatures, AIChE Journal 58(1 ); Sano et al., 1994: "Separation of ethanol/water mixture by silicalite membrane on pervaporation, Journal of Membrane Science 95 (3 ); Hamzah et al., 2013: Pervaporation through NaA zeolite membranes - A review", The Third Basic Science International Conference 2013 ).For the separation of water from gas mixtures at a higher temperature usually hydrophilic membranes are used. These are in particular SiO 2 membranes and zeolite A membranes ( Wang et al., 2011: "Effects of water vapor on gas permeation and separation properties of MFI zeolite membranes at high temperatures, AIChE Journal 58 (1 ); Sano et al., 1994: "Separation of ethanol / water mixture by silicalite membrane on pervaporation, Journal of Membrane Science 95 (3 ); Hamzah et al., 2013: Pervaporation through NaA zeolite membranes - A review, The Third Basic Science International Conference 2013 ).

Bevorzugte Anwendung ist die Entwässerung und Trocknung von Lösemitteldämpfen. Der Einsatz dieser Membranen in der Sabatier-Reaktion zur Abtrennung von Wasser aus einem Gemisch mit Wasserstoff, Kohlendioxid und Methan zeigt jedoch eine unzureichende Selektivität und des Weiteren eine zu geringe Stabilität der Materialien unter den notwendigen Bedingungen der Sabatier-Reaktion. SiO2-Membranen unterliegen bei reduzierenden Bedingungen, wie sie in der Sabatier-Reaktion vorliegen, oberhalb von 100 °C thermischer Degradation ( Damle et al., 1995: "Thermal and chemical degradation of inorganic membrane materials", Technical Report ; Gu et al.: "Hydrothermally stable silica-alumina composite membranes for hydrogen separation", Journal of Membrane Science 310 (1-2): 28 - 37 ) und Zeolith-A-Membranen besitzen mangelnde Stabilität gegenüber sauren Milieus und teilweise limitierte thermische Stabilität ( Hamzah et al., 2013: Pervaporation through NaA Zeolite Membranes - A Review, The Third Basic Science International Conference ; C03; Caro et al., 2009: Why is it so extremely difficult to prepare shapeselective Al-rich zeolite membranes like LTA and FAU for gas separation?, Separation and Purification Technology 66(1): 143 - 147 ), wie sie in Kombination von H2O mit CO2 auftreten.Preferred application is the dewatering and drying of solvent vapors. The use of these membranes in the Sabatier reaction to separate water from a mixture with hydrogen, carbon dioxide and methane, however, shows insufficient selectivity and, furthermore, insufficient stability of the materials under the necessary conditions of the Sabatier reaction. SiO 2 membranes are subject to thermal degradation above 100 ° C. under reducing conditions, as present in the Sabatier reaction (US Pat. Damle et al., 1995: "Thermal and chemical degradation of inorganic membrane materials", Technical Report ; Gu et al .: "Hydrothermally stable silica-alumina composite membranes for hydrogen separation", Journal of Membrane Science 310 (1-2): 28-37 ) and zeolite A membranes have a lack of stability to acidic environments and partially limited thermal stability ( Hamzah et al., 2013: Pervaporation through NaA Zeolite Membranes - A Review, The Third Basic Science International Conference ; C03; Caro et al., 2009: Why Is It So Extremely Difficult to Prepare? Shape-Alike? Zeolite membranes like LTA and FAU for gas separation ?, Separation and Purification Technology 66 (1): 143-147 ), as they occur in combination of H 2 O with CO 2 .

Der Erfindung liegt die Aufgabe zugrunde, eine Möglichkeit zur Verfahrensführung von Gleichgewichtsreaktionen vorzuschlagen, bei denen auf der Seite der Reaktionsprodukte Wasser abgetrennt wird und eine verbesserte Ausbeute an Reaktionsprodukten erzielt wird.The invention has for its object to propose a way to conduct process of equilibrium reactions in which on the side of the reaction products, water is separated and an improved yield of reaction products is achieved.

Die Aufgabe wird durch den Gegenstand des Anspruchs 1 gelöst. Vorteilhafte Ausgestaltungen sind in den abhängigen Ansprüchen angegeben.The object is solved by the subject matter of claim 1. Advantageous embodiments are specified in the dependent claims.

Die Aufgabe wird durch ein Verfahren zur Durchführung von chemischen Gleichgewichtsreaktionen, bei denen Kohlendioxid und Wasserstoff umgesetzt werden, unter Verwendung einer permselektiven Membran gelöst, wobei es sich bei der Gleichgewichtsreaktion entweder um eine Sabatier-Reaktion oder eine Methanol-Herstellungsreaktion handelt, und wobei durch Wirkung der permselektiven Membran Mengenanteile wenigstens eines bei der Reaktion erhaltenen Produkts abgetrennt und der Reaktion entzogen werden. Kennzeichnend für ein erfindungsgemäßes Verfahren ist, dass eine permselektive Membran verwendet wird, die aus einem Material besteht, das eine poröse Struktur mit mittleren Porengrößen von weniger als 0,45 nm (4,5 Ä) aufweist und deren Material wenigstens auf seinen freien Oberflächen hydrophob ist. Als hydrophob wird ein Material angesehen, wenn an einem aufgesetzten Wassertropfen Benetzungswinkel von 85° und darüber gemessen werden. Die chemische Gleichgewichtsreaktion wird unter Anwesenheit eines wasserhaltigen Gasgemisches durchgeführt. Ein wasserhaltiges Gasgemisch ist beispielsweise durch die Produkte der Sabatier-Reaktion Methan und Wasser erhalten. Durch die hohen Temperaturen, bei denen diese Gleichgewichtsreaktion erfolgt, liegt das Wasser als Wasserdampf vor. Eine Mischung von Methan und Wasserdampf wird im Sinne dieser Beschreibung als Gasgemisch, insbesondere als wasserhaltiges Gasgemisch verstanden.The object is achieved by a method for carrying out chemical equilibrium reactions in which carbon dioxide and hydrogen are reacted, using a permselective membrane, wherein the equilibrium reaction is either a Sabatier reaction or a methanol production reaction, and by action the permselective membrane amounts of at least one product obtained in the reaction are separated and removed from the reaction. Characteristic of a method according to the invention is that a permselective membrane is used which consists of a material which has a porous structure with average pore sizes of less than 0.45 nm (4.5 Å) and whose material is hydrophobic at least on its free surfaces is. A material is considered to be hydrophobic if wetting angles of 85 ° and above are measured on an attached water droplet. The chemical equilibrium reaction is carried out in the presence of a water-containing gas mixture. A hydrous gas mixture is obtained, for example, by the products of the Sabatier reaction methane and water. Due to the high temperatures at which this equilibrium reaction takes place, the water is present as water vapor. For the purposes of this description, a mixture of methane and steam is understood as a gas mixture, in particular as a water-containing gas mixture.

Kern der Erfindung ist die Verwendung einer im Wesentlichen aus Kohlenstoff und / oder aus Kohlenwasserstoffen aufgebauten organischen Membran. Vorzugsweise ist die permselektive Membran (fortan auch kurz: Membran) eine Kohlenstoffmembran.The core of the invention is the use of an organic membrane composed essentially of carbon and / or of hydrocarbons. Preferably, the permselective membrane (henceforth also: membrane) is a carbon membrane.

Dabei hat sich überraschend gezeigt, dass durch eine solche Kohlenstoffmembran unter den Bedingungen der Gleichgewichtsreaktion (fortan auch kurz: Reaktion) selektiv Wasser aus dem genannten Gemisch der Produkte abgetrennt wird.It has surprisingly been found that selectively separated from said mixture of products by such a carbon membrane under the conditions of the equilibrium reaction (henceforth also short: reaction).

Die Membran kann dabei beispielsweise auf keramischen Elementen verschiedener Länge und Durchmesser aufgebracht sein, die als Träger fungieren. Die Membranen können auf einer Innenseite und / oder auf einer Außenseite der Träger vorhanden sein. Die Träger können auf der Innenseite und / oder auf der Außenseite Zwischenschichten mit abnehmender Porengröße aufweisen, über denen die Membran angeordnet sein kann. Träger weisen beispielsweise eine Länge von 10 bis 2000 mm, beispielsweise 105 mm und 250 mm, auf. Die Träger können auf ihrer Innenseite und / oder auf ihrer Außenseite teilweise oder vollständig mit der Membran beschichtet sein. Weiterhin können Membranen auf beliebig geformten Trägern von beispielsweise 10 bis 2000 mm, beispielsweise von 500 mm, Länge hergestellt sein. Als zusätzlicher Schritt zur Außenbeschichtung können einseitig verschlossene Keramikträger hergestellt werden und die Membran kann auch auf diesen außenseitig appliziert werden.The membrane can be applied, for example, on ceramic elements of different lengths and diameters, which act as a carrier. The membranes may be present on an inner side and / or on an outer side of the carriers. The carriers may have on the inside and / or on the outside intermediate layers of decreasing pore size, over which the membrane may be arranged. Carriers have, for example, a length of 10 to 2000 mm, for example 105 mm and 250 mm. The carriers can be coated on their inside and / or on their outside partially or completely with the membrane. Furthermore, membranes can be made on any shaped carriers, for example, 10 to 2000 mm, for example, 500 mm in length. As an additional step to the outer coating, one-sided closed ceramic carriers can be produced and the membrane can also be applied to these on the outside.

Bei einer Verwendung teilweise beschichteter Träger ist beispielsweise durch eine konstruktive Maßnahme dafür Sorge zu tragen, dass ein Abtrennen des Wassers nur über die Bereiche des Trägers erfolgt, die von der Membran bedeckt sind.When using partially coated carrier is to ensure, for example, by a constructive measure that a separation of the water takes place only over the areas of the carrier, which are covered by the membrane.

Es ist daher eine bevorzugte Ausführung des erfindungsgemäßen Verfahrens, wenn die permselektive Membran eine Kohlenstoffmembran ist, die Struktur des Materials graphitähnlich und durch Schichten des Materials gebildet ist, die Struktur durch wenigstens eine Folge der Schichten gebildet ist, wobei die Schichten in Ebenen angeordnet vorliegen, zwischen benachbarten Schichten ein mittlerer Abstand der Schichten von weniger als 0,45 nm (4,5 Ä) vorliegt und die Folge der Schichten turbostratisch fehlgeordnet ist.It is therefore a preferred embodiment of the method according to the invention, when the permselective membrane is a carbon membrane, the structure of the material is graphite-like and formed by layers of the material, the structure is formed by at least one sequence of the layers, wherein the layers are arranged in planes, there is a mean interlayer spacing of less than 0.45 nm (4.5 Å) between adjacent layers, and the sequence of layers is disordered turbostratically.

In einer sehr günstigen Ausführung des erfindungsgemäßen Verfahrens ist eine Membran verwendet, bei der wenigstens ein metallhaltiger Katalysator auf einer Oberfläche der permselektiven Membran aufgebracht ist. Dabei bedeutet der Begriff "aufgebracht", dass der Katalysator mit der Membran verbunden ist oder mit dieser in direktem Kontakt steht. Vorzugsweise ist der Katalysator in Form von Partikeln auf einer Oberfläche der Membran gebunden und / oder liegt dieser als Schüttgut an oder auf. Der Katalysator kann auch als eine Beschichtung auf der Membran oder auf Teilen der Membran vorhanden sein.In a very favorable embodiment of the method according to the invention, a membrane is used in which at least one metal-containing catalyst is applied to one surface of the permselective membrane. The term "applied" means that the catalyst is connected to the membrane or is in direct contact with the membrane. Preferably, the catalyst is bound in the form of particles on a surface of the membrane and / or this is as bulk material or on. The catalyst may also be present as a coating on the membrane or on parts of the membrane.

Katalysatoren können dabei metallhaltige Katalysatoren aus einer Gruppe, beinhaltend die Metalle Ruthenium, Nickel, Cobalt, Rhodium, Platin und Palladium oder deren Legierungen, sein. Durch den Begriff der metallhaltigen Katalysatoren sind auch metallische Katalysatoren umfasst.Catalysts may be metal-containing catalysts from a group comprising the metals ruthenium, nickel, cobalt, rhodium, platinum and palladium or their alloys. The term metal-containing catalysts also includes metallic catalysts.

Sehr günstig für die Reaktionsführung und eine hohe Produktausbeute ist es, wenn die chemische Gleichgewichtsreaktion bei einem Wasserstoff-Überschuss bezogen auf den stöchiometrischen Einsatz molekularen Wasserstoffs (H2) durchgeführt wird. So kann der Wasserstoff-Überschuss bezogen auf den stöchiometrischen Einsatz molekularen Wasserstoffs 2,5 % betragen. Durch einen Überschuss an Wasserstoff wird eine unerwünschte Koksbildung weitgehend vermieden.It is very favorable for the reaction procedure and a high product yield if the chemical equilibrium reaction is carried out with an excess of hydrogen based on the stoichiometric use of molecular hydrogen (H 2 ). Thus, the hydrogen excess based on the stoichiometric use of molecular hydrogen can be 2.5%. Excessive hydrogen largely avoids undesirable coke formation.

Als Quelle des molekularen Wasserstoffs können vorteilhaft Gase, wie Biogas, Klärgas, Biomethan, molekularen Wasserstoff enthaltende Kohlendioxidströme, molekularen Wasserstoff freisetzende Elektrolysen, Wasserstoffströme oder Kombinationen dieser Quellen, verwendet werden.As a source of molecular hydrogen, gases such as biogas, sewage gas, biomethane, molecular hydrogen-containing carbon dioxide streams, molecular hydrogen-releasing electrolyses, hydrogen streams, or combinations of these sources can be used to advantage.

Es ist dabei für eine effiziente Verfahrensdurchführung vorteilhaft, wenn die Quellen molekularen Wasserstoffs vor deren Verwendung in dem erfindungsgemäßen Verfahren verfahrenstechnisch behandelt werden. Sie können beispielsweise reduziert und entschwefelt werden, so dass diese ≤ 1 ppm Sauerstoff (02) und Schwefel (S) enthalten und eine Einspeisequalität sichergestellt wird.It is advantageous for efficient process implementation if the sources of molecular hydrogen are treated in terms of process technology before they are used in the process according to the invention. For example, they can be reduced and desulfurized to contain ≤ 1 ppm of oxygen (02) and sulfur (S), ensuring feed-in quality.

Die chemische Gleichgewichtsreaktion ist vorzugsweise entweder eine Sabatier-Reaktion oder eine Methanol-Herstellungsreaktion.The chemical equilibrium reaction is preferably either a Sabatier reaction or a methanol production reaction.

Das erfindungsgemäße Verfahren, insbesondere die Sabatier-Reaktion, wird vorzugsweise bei einem Druck, ausgewählt aus einem Bereich von 1 bis einschließlich 100 bar, z. B. 5, 75, 100 bar, und bei einer Temperatur, ausgewählt aus einem Bereich von 150 bis einschließlich 600 °C, z. B. 400, 500 °C, durchgeführt.The process of the invention, in particular the Sabatier reaction, is preferably carried out at a pressure selected from a range of 1 to 100 bar inclusive, e.g. B. 5, 75, 100 bar, and at a temperature selected from a range of 150 to 600 ° C inclusive, z. B. 400, 500 ° C performed.

Es hat sich als günstig erwiesen, dass die Sabatier-Reaktion bei einem Druck, ausgewählt aus einem Bereich von 10 bis 20 bar, und bei einer Temperatur, ausgewählt aus einem Bereich von 250 bis 450 °C, durchgeführt wird. Insbesondere kann die Sabatier-Reaktion effizient bei einem Druck von 20 bar und bei einer Temperatur von 300 °C durchgeführt werden.It has been found to be favorable that the Sabatier reaction is carried out at a pressure selected from a range of 10 to 20 bar and at a temperature selected from a range of 250 to 450 ° C. In particular, the Sabatier reaction can be carried out efficiently at a pressure of 20 bar and at a temperature of 300 ° C.

Ist die chemische Gleichgewichtsreaktion eine Methanol-Herstellungsreaktion, wird diese vorzugsweise bei einem Druck ausgewählt aus einem Bereich von 80 bis einschließlich 250 bar und bei einer Temperatur ausgewählt aus einem Bereich von 150 bis einschließlich 400° C durchgeführt.When the chemical equilibrium reaction is a methanol production reaction, it is preferably conducted at a pressure selected from a range of 80 to 250 bar inclusive and at a temperature selected from a range of 150 to 400 ° C inclusive.

Methanol (CH3OH) ist als einfachster Vertreter der Stoffgruppe der Alkohole eine der meisthergestellten organischen Chemikalien und dient als Ausgangsstoff vieler weiterer chemischer Produkte (z. B. Formaldehyd, Ameisensäure usw.). Die technische Herstellung erfolgt hauptsächlich durch eine katalytisch unterstützte Reaktion von CO und H2. Die Verfahren zur Methanol-Herstellung werden nach den vorherrschenden Reaktionsdrücken in Hochdruckverfahren (250-350 bar, ∼370 °C), Mitteldruckverfahren (100-250 bar, ∼220-300 °C) und Niederdruckverfahren (50-100 bar, 200-300 °C) unterteilt. Aufgrund ökonomischer Nachteile wird das Hochdruckverfahren heutzutage nicht mehr angewendet. Es werden im Stand der Technik weitestgehend Kupfer-Zink-Katalysatoren auf Aluminiumoxid genutzt.Methanol (CH 3 OH), as the simplest representative of the substance group of alcohols, is one of the most frequently produced organic chemicals and serves as the starting material for many other chemical products (eg formaldehyde, formic acid, etc.). The technical production is carried out mainly by a catalytically assisted reaction of CO and H 2 . The processes for methanol production are based on the prevailing reaction pressures in high pressure processes (250-350 bar, ~370 ° C), medium pressure (100-250 bar, ~220-300 ° C) and low pressure processes (50-100 bar, 200-300 ° C). Due to economic disadvantages, the high pressure process is no longer used today. It is widely used in the prior art copper-zinc catalysts on alumina.

Eine alternative Variante zur Herstellung von CH3OH ist die Reaktion von CO2 mit H2, um auch bei der Synthese dieser Grundchemikalie auf das bisherige Abfallprodukt CO2 zurückgreifen zu können. Bei dieser Reaktion entsteht neben CH3OH auch H2O. Im Vergleich zur Erzeugung von Methanol aus Synthesegas liegt die Produktivität bei der Erzeugung aus CO2 und H2 um den Faktor 3-10 geringer, da das Wasser die Reaktion behindert. Allerdings kann mit einer kontinuierlichen Abführung des Reaktionsproduktes Wasser die Ausbeute erhöht werden. Dies wird durch den Einsatz der Membranen erreicht.An alternative variant for the production of CH 3 OH the reaction of CO 2 with H 2 in order to have access to the existing waste product CO 2 in the synthesis of these basic chemical. In this reaction, in addition to CH 3 OH also H 2 O. In comparison to the production of methanol from synthesis gas, the productivity of the production of CO 2 and H 2 by a factor of 3-10 is lower, since the water hinders the reaction. However, with a continuous removal of the reaction product, the water yield can be increased. This is achieved by using the membranes.

Die Membranen können in flexibler Geometrie verwendet werden. Die Membranen erlauben eine selektive Abtrennung von Wasser unter Prozessbedingungen. Ausgestattet mit einem für die durchzuführende chemische Gleichgewichtsreaktion aktiven Katalysator kann die Ausbeute signifikant erhöht und die Erreichung der Einspeisequalität erleichtert werden.The membranes can be used in flexible geometry. The membranes allow selective separation of water under process conditions. Equipped with an active catalyst for the chemical equilibrium reaction to be carried out, the yield can be significantly increased and the achievement of the feed quality can be facilitated.

Durch ein erfindungsgemäßes Verfahren unter Verwendung organischer Membranen mit hydrophoben Oberflächen wird vorteilhaft selbst bei hohen Temperaturen selektiv Wasser aus der Reaktion abtrennt. Ein verwendeter Katalysator kann dabei als Schüttgut auf der Membran angeordnet sein oder es wird eine katalytisch aktive Membran verwendet. Bevorzugter Einsatz der Membran ist die Umsetzung von Kohlendioxid und Wasserstoff zu Methan (Sabatier-Reaktion) oder Methanol.By a method according to the invention using organic membranes having hydrophobic surfaces, it is advantageous to selectively separate water from the reaction, even at high temperatures. A catalyst used can be arranged as bulk material on the membrane or it is a catalytically active Membrane used. Preferred use of the membrane is the conversion of carbon dioxide and hydrogen to methane (Sabatier reaction) or methanol.

Die erfindungsgemäße Verwendung der beschriebenen Membranen wird beispielsweise zur Wasserabtrennung aus der Sabatier-Reaktion genutzt. Dazu ist ein direkter Kontakt zwischen wasserabtrennender Membran und Katalysator sinnvoll. Die trennaktive Membran kann als Katalysatorträger dienen. Der Katalysator oder ein Katalysatorvorläufer wird auf die trennaktive Schicht aufgebracht und gegebenenfalls in geeigneter Form, beispielsweise durch Wärmezufuhr, aktiviert. Die Aktivierung des Katalysators erfolgt beispielsweise unter Reaktionsbedingungen der Sabatier-Reaktion.The use according to the invention of the membranes described is used, for example, for the removal of water from the Sabatier reaction. For this purpose, a direct contact between water-separating membrane and catalyst makes sense. The separation-active membrane can serve as a catalyst carrier. The catalyst or catalyst precursor is applied to the release-active layer and optionally activated in a suitable form, for example by heat. The activation of the catalyst takes place, for example, under the reaction conditions of the Sabatier reaction.

Die erfindungsgemäße Verwendung der beschriebenen Membranen erlaubt es außerdem, effizient eine chemische Gleichgewichtsreaktion durchzuführen, bei der aus Kohlendioxid und Wasserstoff auf der Eduktseite Methanol und Wasser auf der Produktseite gewonnen werden. Durch die selektive Abtrennung von Wasser wird das Gleichgewicht in Richtung auf die Produkte verschoben und die Bildung von Methanol begünstigt.The use according to the invention of the membranes described also makes it possible to efficiently carry out a chemical equilibrium reaction in which methanol and water are recovered on the product side from carbon dioxide and hydrogen on the educt side. The selective separation of water shifts the equilibrium towards the products and promotes the formation of methanol.

Für das erfindungsgemäße Verfahren werden nachfolgend Ausführungsbeispiele angegeben.For the inventive method embodiments are given below.

1. Reaktion ohne Membran:1st reaction without membrane:

Als Katalysator dient ein Aluminium-unterstütztes Nickeloxid, beispielsweise das kommerziell verfügbare Produkt METH 134. Der Katalysator wurde als Schüttung appliziert und in einem Wasserstoff-/Stickstoffstrom (1:9) entsprechend aktiviert. Der Eduktvolumenstrom beträgt insgesamt ca. 250 Nl/h (Normliter je Stunde). Das H2/CO2-Verhältnis beträgt 4,1:1 (19,6 Vol% CO2, 80,4 Vol% H2) bei einem Prozessdruck von 20 barÜ (20 bar Überdruck) und Reaktionstemperaturen von 275 - 450 °C. Es werden Umsätze zwischen 85 und 89 % bei einer CH4-Selektivität von > 99 % erreicht. Die CH4-Ausbeute beträgt ebenfalls zwischen 85 und 89 %.The catalyst used is an aluminum-supported nickel oxide, for example the commercially available product METH 134. The catalyst was applied as a bed and activated accordingly in a stream of hydrogen / nitrogen (1: 9). The educt volume flow is approximately 250 Nl / h (standard liters per hour). The H 2 / CO 2 ratio is 4.1: 1 (19.6 vol% CO 2 , 80.4 vol% H 2 ) at a process pressure of 20 bar (20 bar overpressure) and reaction temperatures of 275-450 ° C , Revenues of between 85 and 89% are achieved with> 99% CH 4 selectivity. The CH 4 yield is also between 85 and 89%.

2. Reaktion mit Membran2nd reaction with membrane

Als Katalysator dient ein Aluminium-unterstütztes Nickeloxid, beispielsweise das kommerziell verfügbare Produkt METH 134 (Hersteller Clariant). Der Katalysator wurde als Schüttung appliziert und in einem Wasserstoff-/Stickstoffstrom (1:9) entsprechend aktiviert. Der Eduktvolumenstrom beträgt insgesamt ca. 250 Nl/h. Das H2/CO2-Verhältnis beträgt 4,1:1 (19,6 Vol% CO2, 80,4 Vol% H2) bei einem Prozessdruck von 20 barÜ und Reaktionstemperaturen von 240 - 450 °C. Die Raumgeschwindigkeit an der Membran beträgt ∼21,5 s-1 bzw. entspricht einer Lineargeschwindigkeit von ∼0,04 m/s. Es werden Umsätze > 90 % bei einer CH4-Selektivität von > 99 % erreicht. Die CH4-Ausbeute beträgt ebenfalls > 90 %.The catalyst used is an aluminum-supported nickel oxide, for example the commercially available product METH 134 (manufacturer Clariant). The catalyst was applied as a bed and activated in a hydrogen / nitrogen stream (1: 9) accordingly. The educt volume flow is approximately 250 Nl / h in total. The H 2 / CO 2 ratio is 4.1: 1 (19.6 vol% CO 2 , 80.4 vol% H 2 ) at a process pressure of 20 bar and reaction temperatures of 240-450 ° C. The space velocity at the membrane is ~21.5 s -1 or corresponds to a linear velocity of ~0.04 m / s. Revenues> 90% are achieved with a CH 4 selectivity of> 99%. The CH 4 yield is also> 90%.

3. Reaktion mit Membran (katalysatorbeschichtet)3. Reaction with membrane (catalyst coated)

Als Katalysatorvorläufer wird eine Beschichtung der Membran mit Nickeloxid verwendet. Dieser Vorläufer wird in einem Wasserstoff-/Stickstoffstrom (1:9) zum aktiven metallischen Nickel reduziert und entsprechend aktiviert. Der Eduktvolumenstrom beträgt insgesamt ca. 1000 Nl/h. Das H2/CO2-Verhältnis beträgt 4,1:1 (19,6 Vol% CO2, 80,4 Vol% H2) bei einem Prozessdruck von 20 barÜ und Reaktionstemperaturen von 240 - 450 °C. Die Raumgeschwindigkeit an der Membran beträgt ∼58 s-1 bzw. entspricht einer Lineargeschwindigkeit von ∼0,02 m/s. Es werden Umsätze > 95 % bei einer CH4-Selektivität von > 99 % erreicht. Die CH4-Ausbeute beträgt ebenfalls > 95 %.As catalyst precursor, a coating of the membrane with nickel oxide is used. This precursor is reduced in a stream of hydrogen / nitrogen (1: 9) to the active metallic nickel and activated accordingly. The educt volume flow is about 1000 Nl / h in total. The H 2 / CO 2 ratio is 4.1: 1 (19.6 vol% CO 2 , 80.4 vol% H 2 ) at a process pressure of 20 bar and reaction temperatures of 240-450 ° C. The space velocity at the membrane is ~58 s -1 or corresponds to a linear velocity of ~0.02 m / s. Revenues> 95% are achieved with a CH 4 selectivity of> 99%. The CH 4 yield is also> 95%.

Claims (12)

  1. Method for carrying out chemical equilibrium reactions in which carbon dioxide and hydrogen are converted, using a permselective membrane, wherein quantitative proportions of at least water as one of products obtained in the reaction are separated and removed from the reaction through the action of the permselective membrane, characterized in that the equilibrium reaction is either a Sabatier reaction or a methanol production reaction and a permselective membrane is used which is made from a material containing at least carbon and / or hydrocarbons, said material having a porous structure with mean pore sizes of less than 0.45 nm (4.5 Å) and being hydrophobic at least on the free surfaces thereof.
  2. Method according to claim 1, characterized in that
    - the permselective membrane is a carbon membrane,
    - the structure of the material is graphite-like and is formed by layers of the material,
    - the structure is formed by at least one series of layers, wherein the layers are arranged in planes,
    - there is a mean spacing of the layers of less than 0.45 nm (4.5 Å) between adjacent layers, and
    - the series of layers is turbostratically disordered.
  3. Method according to one of claims 1 or 2, characterized in that at least one metal-containing catalyst is arranged on a surface of the permselective membrane.
  4. Method according to claim 3, characterized in that metal-containing catalysts are selected from a group comprising the metals ruthenium, nickel, cobalt, rhodium, platinum and palladium, or alloys thereof.
  5. Method according to one of the preceding claims, characterized in that the chemical equilibrium reaction is carried out with a hydrogen surplus with respect to the stoichiometric use of molecular hydrogen.
  6. Method according to claim 5, characterized in that the hydrogen surplus amounts to 2.5% with respect to the stoichiometric use of molecular hydrogen.
  7. Method according to one of the preceding claims, characterized in that biogas, sewage gas, biomethane, molecular hydrogen-containing carbon dioxide streams, molecular hydrogen-releasing electrolysis, hydrogen streams or combinations thereof are used as sources of molecular hydrogen.
  8. Method according to claim 7, characterized in that the sources of molecular hydrogen are reduced and desulfurized and contain ≤ 1 ppm of oxygen (O2) and sulfur (S).
  9. Method according to claim 1, characterized in that the chemical equilibrium reaction is the Sabatier reaction, and this Sabatier reaction is carried out at a pressure selected from a range of 1 to 100 bar and at a temperature selected from a range of 150 to 600 °C.
  10. Method according to claim 9, characterized in that the Sabatier reaction is carried out at a pressure selected from a range of 10 to 20 bar and at a temperature selected from a range of 250 to 450 °C.
  11. Method according to claim 10, characterized in that the Sabatier reaction is carried out at a pressure of 20 bar and at a temperature of 300 °C.
  12. Method according to claim 1, characterized in that the chemical equilibrium reaction is a methanol production reaction and is carried out at a pressure selected from a range of 80 bar up to and including 250 bar and at a temperature selected from a range of 150 °C up to and including 400 °C.
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DE102014118894A1 (en) 2016-07-07
US9611187B2 (en) 2017-04-04
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